Cadmium-free quantum dots, tunable quantum dots, quantum dot containing polymer, articles, films, and 3D structure containing them and methods of making and using them

Abstract

Quantum dots that are cadmium-free and/or stoichiometncally tuned are disclosed, as are methods of making them. Inclusion of the quantum dots and others in a stabilizing polymer matrix is also disclosed. The polymers are chosen for their strong binding affinity to the outer layers of the quantum dots such that the bond dissociation energy between the polymer material and the quantum dot is greater than the energy required to reach the melt temperature of the cross-linked polymer.

What is claimed is: 
     
       1. A nanocrystal polymer composite comprising a plurality of capped ZnInCuS semiconductor nanocrystals dispersed in a polymer resin, wherein,
 the capped ZnInCuS semiconductor nanocrystals comprise:
 a core comprising ZnInCuS, wherein the core is modified with a zinc alkylcarboxylate or a dialkyl zinc; 
 a first cap layer overlying the core, wherein the first cap layer comprises ZnS; 
 a second cap layer overlying the first cap layer, wherein the second cap layer comprises Al 2 O 3 ; 
 the capped ZnInCuS semiconductor nanocrystals are configured to emit radiation in a range from 530 nm to 750 nm; and 
 the polymer resin comprises an acrylate resin, wherein the acrylate resin is derived from homopolymers of cyclohexyl acrylate and cyclohexyl acrylate copolymer with methyl methacrylate or heptyl acrylate. 
 
 
     
     
       2. The nanocrystal polymer composite of  claim 1 , wherein the acrylate resin comprises from 25 wt % to 100 wt % of cyclohexyl acrylate, wherein wt % is based on the total weight of the acrylate resin. 
     
     
       3. The nanocrystal polymer composite of  claim 1 , wherein the acrylate resin is derived from heptyl acrylate, cyclohexyl acrylate, and trimethylolpropane triacrylate. 
     
     
       4. The nanocrystal polymer composite of  claim 1 , wherein the polymer resin is derived from a nitrogen-containing monomer, wherein the nitrogen-containing monomer comprises a nitrogen-containing monomer having the structure of Formula (II), Formula (III), Formula (IV), Formula (V), or a combination of any of the foregoing: 
       
         
           
           
               
               
           
         
         wherein,
 each of R 3  and R 4  is independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, iso-pentyl, C 6  to C 12  linear, branched, cyclic or aromatic hydrocarbyl, and polyethylene glycol; and 
 R 5  is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, iso-pentyl, C 6  to C 12  linear, branched, cyclic or aromatic hydrocarbyl, and polyethylene glycol. 
 
       
     
     
       5. The nanocrystal polymer composite of  claim 1 , wherein the core is modified with a zinc alkyl carboxylate. 
     
     
       6. The nanocrystal polymer composite of  claim 1 , wherein the core is modified with a dialkyl zinc. 
     
     
       7. The nanocrystal polymer composite of  claim 1 , wherein a bond dissociation energy between the polymer resin and the Al 2 O 3  layer is greater than the energy required to reach the melt temperature of the polymer resin when cross-linked. 
     
     
       8. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite comprises from 0.0001 wt % to 75 wt % of the capped ZnInCuS semiconductor nanocrystals, wherein wt % is based on the total weight of the nanocrystal polymer composite. 
     
     
       9. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite is cured. 
     
     
       10. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite is uncured. 
     
     
       11. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite comprises a down conversion film. 
     
     
       12. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite comprises a three-dimensional structure. 
     
     
       13. The nanocrystal polymer composite of  claim 1 , wherein the nanocrystal polymer composite comprises a solution, an ink, a film, a resin pellet, or a thermoplastic pellet. 
     
     
       14. An optical device comprising the nanocrystal polymer composite of  claim 1 . 
     
     
       15. An optoelectronic device comprising the nanocrystal polymer composite of  claim 1 . 
     
     
       16. The nanocrystal polymer composite of  claim 1 , wherein the polymer resin is derived from homopolymers of cyclohexyl acrylate and cyclohexyl acrylate copolymers with methyl methacrylate or heptyl acrylate, wherein the homopolymers and copolymers comprise repeating carbonyl units oriented in three-dimensional space such that the electronegative carbonyl oxygen repeat distance matches a repeat distance of electropositive regions on a surface of the Al 2 O 3  cap layer. 
     
     
       17. The nanocrystal composite of  claim 1 , wherein the zinc alkylcarboxylate is zinc acetate. 
     
     
       18. The nanocrystal composite of  claim 1 , wherein the dialkyl zinc is dimethyl zinc.